Monoazo dyestuffs



3,335,126 MONOAZO DYESTUFFS Thomas Douglas Baron and Brian RibbonsFishwick, Manchester, England, assignors to Imperial Chemical IndustriesLimited, London, England, a corporation of Great Britain No Drawing.lFiled Nov. 2, 1964, Ser. No. 408,365 Claims priority, application GreatBritain, Nov. 14, 1963, 45,046/ 63 3 Claims. (Cl. 260--207.1)

This invention relates to new monoazo dyestuffs and more particularly itrelates to new water-insoluble monoazo dyestuffs which are valuable forcolouring synthetic textile materials, in particular polyester textilematerials.

According to the invention there are provided the water-insolublemonoazo dyestuffs of the formula:

C o o R Y A. c R OzN N=N N\ W l A. B

wherein A and A each independently represent lower alkylene radicals;

B represents a hydrogen atom or a cyano, hydroxy or COOR radical;

R represents a hydrogen atom or a lower alkyl or hydroxy lower alkylradical;

Z represents a hydrogen atom or a lower alkyl or lower alkoxy radical;

Y represents a hydrogen, chlorine or bromine atom or a lower alkyl,lower alkoxy or NH acyl radical, wherein acyl is the radical of acarboxylic, carbarnic or organic carbonic acid;

W represents a hydrogen atom or a COOR radical;

X represents a hydrogen, chlorine or bromine atom or a nitro group, orwhen W represents a hydrogen atom X may also represent a COOR radical;and

R represents a lower alkyl, hydroxy lower alkyl, chloro lower alkyl,bromo lower alkyl or lower alkoxy lower alkyl radical.

The lower alkylene radicals represented by A and A are alkylene radicalscontaining not more than 6 carbon atoms such as methylene, trimethylene,propylene, tetramethylene, azfi-dimethylethylene and, preferably,ethylene radicals.

Throughout this specification the terms lower alkyl and lower alkoxy areused to denote alkyl and alkoxy radicals respectively of low molecularweight, in particular alkyl and alkoxy radicals containing from 1 to 4carbon atoms.

As examples of the radicals represented by R there may be mentionedmethyl, ethyl, propyl, butyl, p-hydroxyethyl and or 'y-hydroxypropylradicals: it is however preferred that R represents a lower alkylradical.

As examples of the radicals represented by R there may be mentionedmethyl, ethyl, propyl, butyl, fi-hydroxyethyl, 5- or -hydroxypropyl,fi-chloroethyl, B-bromoethyl, fi-methoxyethyl, B-ethoxyethyl,-methoxypropyl and 'y-ethoxypropyl radicals: it is however preferredthat R represents a lower alkyl radical.

As examples of the lower alkyl radicals represented by Z and Y there maybe mentioned ethyl, propyl and preferably methyl radicals; and asexamples of the lower alkoxy radicals represented by Z and Y there maybe mentioned ethoxy, propoxy and preferably methoxy radicals. Asexamples of the acyl radicals present in the --NH acyl radicalrepresented by Y there may be mentioned acyl radicals derived fromaliphatic carboxylic acids, in particular lower aliphatic carboxylicacids such as formic States Fatent C 3,335,126 Patented Aug." 8, 1967acid, acetic acid, propionic acid and butyric acid, which, if desired,may contain substituents such as chlorine atoms or cyano, lower alkoxysuch as methoxy, or carbo lower alkoxy such as carbomethoxy groups; acylradicals derived from monocyclic aromatic carboxylic acids such asbenzoic acid or toluic acid which may, if desired, contain substituentssuch as chlorine or bromine atoms or nitro, lower alkoxy such asmethoxy, carbo lower alkoxy such as carbomethoxy, and acylamino such asacetylamino groups; acyl radicals derived from carbamic acids such asaminocarbonyl, N-lower alkyl aminocarbonyl and phenylcarbonyl radicals;and acyl radicals derived from organic carbonic acids such as loweralkoxy carbonyl and phenoxycarbonyl radicals.

It is however preferred that the acylamino group represented by Y is agroup of the formula: NHCOR wherein R represents a hydrogen atom or alower alkyl radical.

It is also preferred that W represents a hydrogen atom; and also that Brepresents a CN or -COOR radical.

According to a further feature of the invention there is provided aprocess for the manufacture of the waterinsoluble monoazo dyestuffs, ashereinbefore defined, which comprises coupling a diazotised primaryamine of the formula C OOR OzN- NH:

Formula I with a coupling component of the formula:

/A- 0 00B l A" B Z Formula II wherein A, A, B, R, R, W, X, Y and Z havethe meanings stated above.

The process of the invention may be conveniently brought out by addingan aqueous solution or suspension of the diazotised primary amine to asolution of the coupling component in a dilute aqueous solution of anacid such as hydrochloric acid, stirring the resulting mixture,preferably at a pH between 3 and 7, to effect formation of the monoazodyestuff, and finally isolating the monoazo dyestuif by conventionalmethods.

As specific examples of the primary amines of Formula I there may bementioned methyl 2-amino-5-nitrobenzoate,

methyl 2-amino-3-(chloroor bromo-)-5-nitrobenzoate, methyl 2-amino-3:S-dinitrobenzoate,

ethyl 2-amino-3 :S-dinitrobenzoate, n-propyl 2-amino-3:S-dinitrobenzoate, B-chloroethyl Z-amino-S-nitrobenzoate, ,B-bromoethyl2-amino-5-nitrobenzoate, S-hydroxypropyl 2-amino-5-nitrobenzoate,B-methoxyethyl 2-amino-5-nitrobenzoate, dimethyl2-amino-5nitroisophthalate, dimethyl Z-amino5-nitroterephthlate anddimethyl 3-amino-6-nitrophthalate.

The coupling components of Formula II may themselves be obtained byreacting a'secondary amine of the formula:

with the appropriate ester of a chloroor bromo-lower aliphaticcarboxylic acid, or by reacting a secondary amine of the formula:

I A-COOR with a compound of the formula: CLAB.

As specific examples of the coupling components of Formula II there maybe mentioned N- B-cyanoethyl) -N- (fi-carboxyethyl) aniline,

N-ethyl-N- B-methoxycarbonylethyl) aniline,

N-( ,B-hydroxyethyD-N- (,B-ethoxycarbonylethyl) aniline,

N N-bis (B-methoxycarbonylethyl) aniline,

2 S-dimethyl-N N-bis 'y-methoxycarbonylpropyl) aniline,

2: S-dimethoxy N N-bis'( B-ethoxycarbonylethyl) aniline,

2-methoxy-5 -methyl-N (,B-cyanoethyl) -N- B-methoxycarbonylethyl)aniline,

N- B-cyanoethyl) -N- (fi-ethoxycarbonylethyl) -m- (chloroorbromoaniline,

N N-bis- ([i-ethoxycarbonylethyl -m-aminoacetanilide,

2-methoxy-S-propionylamino-N N-bis- (/if-methoxycarbonylethyl) anilineand 2-methy1-5 -formylamino-N- B-cyanoethyl) -N- ,6-

methoxycarbonylethyl aniline.

The monoazo dyestuffs, as hereinbefore defined, are valuable forcolouring synthetic textile materials, for example cellulose acetatetextile materials such as secondary cellulose acetate and cellulosetriacetate textile materials, polyamide textile materials such aspolyhexamethyleneadipamide textile materials, and preferably aromaticpolyester textile materials such as polyethylene terephthalate textilematerials. Such textile materials can be be in the form of thread, yarn,or woven or knitted fabric. 1

Such textile materials can conveniently be coloured with. the monoazodyestuffs, as hereinbefore defined, by immersing the textile material ina dyebath comprising an aqueous dispersion of one or more of the saiddyestuffs, which dyebath preferably contains a non-ionic, cationicand/or anionic surface-active agent, and thereafter heating the dyebathfor a period at a suitable temperature. In the case of secondarycellulose acetate textile materials it is preferred to carry out thedyeing process at a temperature between 60 and 85 C.; in the case ofcellulose triacetateor polyamide textile material it is preferred tocarry out the dyeing process at 95 to 100 C.; in the case of aromaticpolyester textile materials the dyeing process can either be carried outat a temperature between 90 and 100 C., preferably in the presence of acarrier such as diphenyl or o-hydroxydiphenyl, or at a temperature above100 (3., preferably at a temperature between 120 and 130 C., undersuperatmospheric pressure.

Alternatively the aqueous dispersion of the said monoazo dyestuff can beapplied to the textile material by a padding or printing process,followed by heating or steaming of the textile material. In suchprocesses it is preferred to incorporate a thickening agent, such as gumtragacanth, gum arabic or sodium alginate, into the aqueous dispersionof the said monoazo dyestuff.

At the conclusion of the colouring process it is preferred to give thecoloured textile material a rinse in water or a brief soaping treatmentbefore finally drying 4 the coloured textile material. In the case ofaromatic polyester textile materials it is also preferred to subject thecoloured textile material to a treatment in an alkaline aqueous solutionof sodium hydrosulphite before the soaping treatment in order to removeloosely attached dyestuff from the surfaceofthe textile material.

The monoazo dyestuffs have excellent affinity and building up propertieson synthetic textile materials, and in particular on aromatic polyestertextile materials, so enabling deep shades to be obtained. The resultingcolourations which range in shade from orange to blue, have excellentfastness to light, to wet treatments, and, in particular, to dry heattreatments such as those carried out at high temperatures duringpleating operations.

One preferred class of the monoazo dyestuffs of the invention comprisesthe monoazo dyestuffs of the formula:

000m Y A.C o o R oiN- N=N N\ ALB X1 2 wherein A, A B, Y and Z have themeanings stated, R and R each independently represent lower alkylradicals, and X represents a hydrogen, chlorine or bromine atom or anitro group. The dyestuffs of this class have good build up propertieson polyethylene terephthalate textile materials and the resultingcolourations have excellent fastness properties.

A second preferred class of the monoazo dyestuffs of the inventioncomprises the monoazo dyestuffs of the formula:

I A. c 0 o R 02N- N=N -N A B1 X 2 wherein A, A Y, Z, R", R and X havethe meanings stated and B represents -CN or COOR The dyestuffs of thisclass when applied to polyethylene terephthalate textile materials yieldcolourations having.

excellent fastness to light.

A third preferred class of the monoazo dyestuffs of the inventioncomprises the monoazo dyestuffs of the formula:

COOR Y ALCN A.C 0 0R OzN- wherein A, A R and R have the meanings statedand Y represents a hydrogen, chlorine or bromine atom or a lower alkylradical.

The dyestuffsjof this class have excellent build up properties onpolyethylene terephthalate textile materials and the resultingcolourations have excellent fastness to light.

A fourth preferred class of the monoazo dyestuffs of the inventioncomprises the monoazo dyestuffs of the formula:

COOR NHCOR Example 1 To a warm solution of 1.96 parts of methylZ-amino-S- nitrobenzoate in parts of acetic acid there are added, withstirring, 2.3 parts of 10 N hydrochloric acid. The mixture is cooled to10 C. and a cooled solution of 0.71 part of sodium nitrite in 5 parts ofwater is quickly added. The mixture is stirred between 5 C. and 10 C.for 10 minutes and any excess nitrous acid is destroyed by addingsulphamic acid.

The following table gives further examples of monoazo dyestuffs of theinvention which are obtained by diazotising the amines listed in thesecond column of the table and coupling the resulting diazo compoundswith the coupling components listed in the third column of the table bymethods similar to that described in Example 1. The fourth column of thetable indicates the shades obtained when the resulting dyestufls areapplied to polyethylene terephthalate textile materials by methodssimilar to that described in Example 2.

Ex. Amine Coupling Component Shade Methyl 2-amin0-5-nitr0benz0ateN-(B-cyanoethyl)-N-(fl-earb0xyethyl)aniline Orange.

d0 T N-(flcyanoethyl)-N-(Bethoxycarbonylethyl)aniline- D0.

Dimethyl Z-ammo-S-mtroterepht halat N -(fi-cyanoethyl)-N-(B-methoxycarbonylethyl) -aniline Reddish orange. Ethyl2-amino-5-nitrobenzoate do Orange. fl-Chloroethyl2-amino-5-nitrobenzoate do Do.

do N-(B-cyanoethyl) -N-(B-ethoxycarbonylethyl) aniline D0. Ethyl2-amino-5-nitrobenzoate. 0 Do. n-Butyl 2-amino-5-nitrobenzoate N -(fl:yanoethyl) -N-(fl-methoxycarbonylethyl) -aniline Do. B-Methoxyethyl2-amino-5-nitrobenzoate .do Do. fi-Hydroxyethyl 2-amino-5-nitrobenzoateDo Dirnethyl Z-amino-5-nitr0is0phthalate Metlilyl 2amino5-nitrobenzoaten :do N-(fi-cyanoethyl) -N-(B-et hyxoc arbonylethyl) -m-toluidine N-(fleyanoethyl) -N-(fi-met hoxycarbonylet hyl) -m-chloroanilin orangebrown. Reddish-Orange. Orange.

N- (fl-cyanoethyl-N- (fi-methoxycarbonylet hyl) -m-bromoani1ine Do.

N N-b s (fl-met hoxyearbonylet hyl) aniline Reddish-orange. N N-bsoi-met hoxycarbonylet hyl)-m-t oluidine Red.

N N-bls (,B-met hoxyearbonylet hyl)-m-ehloroaniline. Orange.

N N -bis (B-methoxyearbonylet hyl) -m-aminoacetanili Bluish-red.

N N-brs (fi-ethoxycarbonylet hyl)-maminoacetanilide. Do.

N N -b1s (fl-met hoxycarbonylet hyl) -maminoiormanilid D0.

Net yl-N-(B-methoxycarbonylethyl) aniline Scarlet N -et hyl-N-(n-butoxycarbonylethyl) aniline Do.

N N-bis- (fl-methoxycarbonylethyl) -rn-anisidine- Red.

N N-b -[fi- 5-hydroxyet hylcarbonyl) ethyl] aniline Reddish-or ange. N-(B-hydroxyethyD-N -(B-methoxycarb0nylethyl) aniline. Do.N-(y-hydroxypropyl) -N- (B-methoxycarbonylet hyl) aniline D0.

N cyanomethyl-N (fl-methoxycarbonylethyl) aniline Orange.

N N-blS (methoxycarbonylmethyl) aniline 0. N-(fl-cyanoet hyl)N-(fl-methoxycarbonylet hyl) aniline Do. N-(fi-cyano ethyl) -N-(fl-methoxycarbonylet hyl) -n1-et hylaniline Reddish-orange. N-(fl-cyano ethyl) -N-(fl-methoxycarbonylet hyl)-m-phenetldine.. Do.

N- (5-cyanobutyl) -N- (B-met hoxycarbonylethyl) aniline". Orange.

N- (fl-cyanoet hyl)-N- (y-methoxyearbonylpropyl) aniline Do.N-(fl-eyanoethyl) -N(6methoxycarbonylbutyl) aniline D0.

The diazo solution so obtained is added during minutes to a solution of2.32 parts of N-(fi-cyanoethylyN- (fi-methoxycarbonylethyl)aniline in amixture of 50 parts of water, 6 parts of a 2 N aqueous solution ofhydrochloric acid and 50 parts of acetone. The mixture is stirred for 6hours, sodium acetate solution is added to raise the pH to about 4 andstirring is continued for a further 24 hours. The dyestufl is thenfiltered oif, reslurried in water and the slurry is basified by additionof sodium carbonate. The product is then refiltered, washed with waterand dried. After recrystallisation from butanol, it has a melting pointof 90 C.

Example 2 A dyebath is prepared by milling 1 part of the dyestulf ofExample 1 with 80 parts of water containing 3 parts of the sodium saltof a sulphonated naphthalene-formaldehyde condensate, and adding thedispersion so obtained in 4000 parts of water containing 1 part oleylsodium sulphate. 100 parts of polyethylene terephthalate fabric isplaced in the dyebath which is then heated to 130 C. for minutes in aclosed vessel. The polyethylene terephthalate fabric is then rinsed inwater and immersed for 15 minutes at 50 C. in an aqueous solutioncontaining 0.2% sodium hydroxide, 0.2% sodium hydrosulphite and 0.1%cetyl trimethyl ammonium bromide. The fabric is again rinsed in waterand then immersed for 15 minutes in a warm aqueous solution of asynthetic detergent, rinsed in water and dried.

The polyethylene terephthalate fabric is dyed an orange shade havinggood fastness to heat treatments and to light.

2.75 parts of methyl 2-amino-3-bromo-5-nitrobenzoate are gradually addedto 15 parts of nitrosyl sulphuric acid (which is obtained by adding 1part of sodium nitrite to 14 parts of sulphuric acid) at 20 to 25 C.,and the mixture is then cooled to 0 C. parts of an aqueous solution ofphosphoric acid of specific gravity 1.65 are then added over 1 hour, thetemperature being maintained between 0 and 5 C. by external cooling. Themixture is stirred for a further hour at 0 C., and 0.5 part of urea isthen added. The resulting solution of the diazo compound is then addedto a solution of 3.52 parts of 2- methoxy 5 acetylaminoNz-N-bis(,B-methoxycarbonylethyl)aniline in a mixture of 60 parts ofacetone and 60 parts of a 0.2 N aqueous solution of hydrochloric acid at5 C. The mixture is stirred for 1 hour at 5 to 10 C., 600 parts of waterare added, and the precipitated dyestulf is filtered off, washed withWater and dried.

When dispersed in aqueous medium the dyestutf so obtained dyespolyethylene terephthalate textile materials in violet shades possessingexcellent fastness properties.

The following table gives further examples of the monoazo dyestuffs ofthe invention which are obtained by diazotising the amines listed in thesecond column of the table and coupling the resulting diazo compoundswith the coupling components listed in the third column of the table bymethods similar to that described in Example 38. The fourth column ofthe table indicates the shades ob- R is selected from the classconsisting of lower alkyl,

tained when the resulting monoazo dyestufis are applied to polyethyleneterephthalate textile materials by methods similar to that described inExample 2,

hydroxy lower alkyl, chloro lower alkyl, bromo lower alkyl and loweralkoxy lower alkyl;

Ex. Amine Coupling Component Shade 39 Methyl 2-amino-3'5-dinitrobenzoater 2-methoxy-5-acetylamino-NN-bis-(B-methoxycarbonylethyl)aniline. Navy-blue.

do 2-methoxy-5-iormylamino-N N-bis- (B-methoxycarb onylethyl) aniline.Reddish-navy.

Methyl Z-amino bromo-5-nitrobenzoate V do Reddish-violet. Methyl2-amino-3-chloro-5-nitrobenzoate.2-Inetlioxy5-acetyla1nino-N:Nbis-(B-methoxycarbonylethyl)aniline.-. Do.43. n-Propyl-2-amino6:5-dinitrobenzoate .do Navy blue. 44.fl-Methoxyethyl Z-amino-S:5-dinitrobenzoate. .do D0.

Methyl 2-amino-3:5-dinitrobenzoate 2-methyl-5-acetylamino-N:N-bis-(B-ethoxycarbonylethyl) aniline Violet.

d 2-methoxy-5-acetylamino-N N-bis-(B-ethoxycarbonylethyl)aniline- Navyblue.

Z-ethoxy-fi-formylamino-N:N-bisifl-methoxyethyl)aniline D0.2-Ilnethoxy-5 -propionylan1ino-N N-bis- (Banethoxyc arbonylethyl) ani-Do.

me. 2-methoxy-5 -b enzoylaInino-N N-bis-(fi-methoxycarb onylet hyl)aniline- Do. 2-metboxy-5-methoxyearbonamido-N :N-bis-(fl-methoxy- Navyblue.

carbonylethyl) aniline. 2-Inet hoxy'5ureido-N: N-bis- (,B-methoxycarbonylethyl) aniline Do. 52 -do2-ethyl-5-a0etylamino-N:Nbis-(fl-methoxycarbonylethyl)aniline Violet.

n-Buty1 Z-annno-B -d1 n 1trobenzoete2-methoxy-5acetylamino-N:N-bis-(B-methoxycarbonylethyl) aniline Navyblue. Methyl 2-am1no-3z5-din1trobenzoate2-methoxy-5-(p-methoxybenzoylarnino)-N:N-bis-(fl-methoxy- Do.

carbonylethybaniline. 55 do 2-methoxy-5-(2 :4-djmet hoxyb enzoylamino)-N: N-bis-(Bmethoxy- Do.

carbonylethyl) aniline. 56 d 2-methoxy-5-(m-nitrobenzoylamino)-N:N-bls-(fl-methoxy- D0.

carbonylethyl) aniline. 57 do2-,meth0xy-5-(m-aeetylaminobenzoylamino)-N:N-bis-(fi-methoxy- Do.

carbonylethybaniline. R do Z-metho xy-5 (p-bromobenzoylamino) N:N-bis-(B-met hoxy- D0 earbonylethyhaniline. 59 Methyl2-amino-3zfi-dinitrobenzoate 2-112?ligxy g(ochlorobenzoylamino)-N:N-bis-(fl-methoxycarbonyl- Do.

e y am me. 60 do n2-methoxy-5-(p-methoxycarbonylbenzoylamino)-N:N-bisQS-methoxy- Do.

carbonylethyDaniline. fil do 2-metihoxy-5-n-butyrylamino-N N-bis-(B-methoxycarbonylet hyl) Do.

am me. 62 fin 2-methoxy-5-trichloroacety1amino-N:N-bis-(B-methoxyethyl)aniline. D0. m do2-methoxy-5-methoxyacetylamino-N:N-bis-(fl-methoxycarbonyl- Do.

ethyl)a.niline. 64 .do 2-methoxy-5-(fi-cyanopropionylamino) -N N-bis-(fi-met hoxyearbonyl- Do.

ethyl) aniline. do v2-met1h0xy-5-methyloxalylamino-N:N-bis-(fl-methoxycarbonyl) Do.

3.111 me. fl-Chloroethyl-2-amino-3:5-dinitrobenz0ate-Z-methoxy-S-acetylamino-N:N-bis-(fl-methoxycarbonylethyl)aniline Do.B-Ethoxyethy1-2-ammo-3:5-d1n1trobenzoate dn g 7 Do. fl-Bromoethyl2-amino-3: 5-dinitrobenzoate. do Do.

What we claim is: 1. The water-insoluble monoazo dyestufis of theformula:

and X is selected from the class consisting of hydrogen, chlorine,bromine and nitro, and when W represents a hydrogen atom X may alsorepresent a COOR C0031 Y radical.

A-COOR 2. The water-insoluble monoazo dyestuffs of the for- N 2 N mula:

W \ALB 000R NHCOR4 wherein OzN- N=.N N (A .o o 0 B A and Aeachindependently represent lower alkylene radicals; N02 )n-1=R B isselected from the class consisting of hydrogen,

cyano, hydroxy and groups of the formula --COOR;'

R is selected from the class consisting of hydrogen,

lower alkyl and hydroxy lower alkyl;

Z is selected from the class consisting of hydrogen,

lower alkyl and lower alkoXy;

Y is selected from the class consisting of hydrogen,

chlorine, bromine, lower alkyl, lower alkoxy and acylamino, and acyl isthe acyl radical of an acid selected from theclass consisting of loweraliphatic carboxylic acids, chloro lower aliphatic carboxylieacids,cyano lower aliphatic carboxylic acids, lower alkoxy lower aliphaticcarboxylic acids, carbo lower'alkoxy aliphatic carboxylic acids, benzoicacid, chlorobenzoic acids, bromobenzoic acids, methoxybenzoic acids,nitrobenzoic acids, lower alkoxy benzoic acids, carho lower alkoxybenzoic acids, acetylamino benzoic acids, aminocarbamic acid, N-loweralkyl aminocarbamic acids, N-phenylarnino. carbamic acid, lower alkoxycarboxylic acids and phenoxy carboxylic acid;

W is selected from the class consisting of a hydrogen atom and a COOR'group;

wherein R R and R each independently represent lower alkyl, and A and Aeach independently represent lower alkylene.

.A.COOR

References Cited FOREIGN PATENTS 910,306 11/ 1962 Great Britain. 7913,899 12/1962 Great Britain.

CHARLES B. PARKER, Primary Examiner.

D. M. PAPUGA, Assistant Examiner.

1. THE WATER-INSOLUBLE MONOAZO DYESTUFFS OF THE FORMULA: